US4107076AExpiredUtility

Catalyst system for catalyzing the water gas shift reaction

31
Assignee: UNIV ROCHESTERPriority: Mar 31, 1977Filed: Mar 31, 1977Granted: Aug 15, 1978
Est. expiryMar 31, 1997(expired)· nominal 20-yr term from priority
Inventors:Richard EisenbergChien-Hong Cheng
B01J 31/04Y02P20/52B01J 2531/822B01J 31/26B01J 31/20C01B 3/16
31
PatentIndex Score
3
Cited by
2
References
33
Claims

Abstract

A method for carrying out the water gas shift reaction by use of a homogeneous catalyst system containing rhodium carbonyl iodide in a water/acetic acid solvent is described. The catalyst system can be formed from [RH (CO)2 Cl]2, aqueous HI and glacial acetic acid. When a reactor is charged under 250-400 torr of CO at 90 DEG C catalysis of the water gas shift reaction results.

Claims

exact text as granted — not AI-modified
What is claimed is 
     
       1. In a method for effecting the water gas shift reaction, the improvement which comprises contacting water and carbon monoxide reactants in the presence of a homogeneous catalyst system at a temperature from about 80° C to less than 95° C, said homogeneous catalyst system being formed essentially by combining [Rh (CO) 2  Cl] 2 , an iodide salt of a non-interacting cation, a strong acid selected from the group consisting of HCl and HBF 4 , water and acetic acid, the ratio of iodide to rhodium being at least 50 to 1 and the ratio of water to hydrogen cations being about 5 to 100 to 1 in said catalyst system, thereby producing hydrogen and carbon dioxide. 
     
     
       2. The invention as set forth in claim 1 wherein said carbon monoxide reactant is introduced to said catalyst system under pressure of from 250 to 400 torr. 
     
     
       3. The invention as set forth in claim 2 wherein said step of introducing said carbon monoxide reactant is carried out with an inert gas such as nitrogen. 
     
     
       4. The invention as set forth in claim 1 wherein rhodium in the (I) oxidation state is present in said catalyst system. 
     
     
       5. The invention as set forth in claim 1 wherein rhodium in the (III) oxidation state is present in said catalyst system. 
     
     
       6. The invention as set forth in claim 1 wherein the concentration of rhodium in said catalyst system is of the order of 0.01 molar. 
     
     
       7. The invention as set forth in claim 1 wherein said acetic acid is glacial acetic acid. 
     
     
       8. The invention as set forth in claim 1 wherein the concentration of said strong acid in said system is from 1 to 5 molar. 
     
     
       9. The invention as set forth in claim 1 wherein said cation is sodium and said iodide salt is NaI. 
     
     
       10. In a method for effecting the water gas shift reaction, the improvement which comprises contacting water and carbon monoxide reactants in the presence of a homogeneous catalyst system at a temperature from about 80° C to less than 95° C, said homogeneous catalyst system being formed essentially by combining [Rh(CO) 2  Cl] 2 , aqueous HI, and acetic acid, the ratio of iodide to rhodium being at least 50 to 1 and the ratio of water to hydrogen cations being about 5 to 100 to 1 in said catalyst system, thereby producing hydrogen and carbon dioxide. 
     
     
       11. The invention as set forth in claim 10 wherein said carbon monoxide reactant is introduced to said catalyst system under pressure of from 250 to 400 torr. 
     
     
       12. The invention as set forth in claim 11 wherein said step of introducing said carbon monoxide reactant is carried out with an inert gas such as nitrogen. 
     
     
       13. The invention as set forth in claim 10 wherein rhodium in the (I) oxidation state is present in said catalyst system. 
     
     
       14. The invention as set forth in claim 10 wherein rhodium in the (III) oxidation state is present in said catalyst system. 
     
     
       15. The invention as set forth in claim 10 wherein the concentration of rhodium in said catalyst system is of the order of 0.01 molar. 
     
     
       16. The invention as set forth in claim 10 wherein said acetic acid is glacial acetic acid. 
     
     
       17. The invention as set forth in claim 10 wherein the concentration of HI in said system is from 1 to 5 molar. 
     
     
       18. In a method for effecting the water gas shift reaction, the improvement which comprises contacting water and carbon monoxide reactants in the presence of a homogeneous catalyst system at a temperature from about 80° C to less than 95° C, said homogeneous catalyst system being formed essentially by combining [RhI 5  (CO)] -2  X 2  where X is the non-interacting cation tetra butyl ammonium, an iodide salt of a non-interacting cation, a strong acid selected from the group consisting of HCl and HBF 4 , water and acetic acid, the ratio of iodide to rhodium being at least 50 to 1 and the ratio of water to hydrogen cations being about 5 to 100 to 1 in said catalyst system thereby producing hydrogen and carbon dioxide. 
     
     
       19. The invention as set forth in claim 18 wherein said carbon monoxide reactant is introduced to said catalyst system under pressure of from 250 to 400 torr. 
     
     
       20. The invention as set forth in claim 19 wherein said step of introducing said carbon monoxide reactant is carried out with an inert gas such as nitrogen. 
     
     
       21. The invention as set forth in claim 18 wherein rhodium in the (I) oxidation state is present in said catalyst system. 
     
     
       22. The invention as set forth in claim 18 wherein rhodium in the (III) oxidation state is present in said catalyst system. 
     
     
       23. The invention as set forth in claim 18 wherein the concentration of rhodium in said catalyst system is of the order of 0.01 molar. 
     
     
       24. The invention as set forth in claim 18 wherein said acetic acid is glacial acetic acid. 
     
     
       25. The invention as set forth in claim 18 wherein the concentration of said strong acid in said system is from 1 to 5 molar. 
     
     
       26. The invention as set forth in claim 18 wherein said cation is sodium and said iodide salt is NaI. 
     
     
       27. In a method for effecting the water gas shift reaction, the improvement which comprises contacting water and carbon monoxide reactants in the presence of a homogeneous catalyst system at a temperature from about 80° C to less than 95° C, said homogeneous catalyst system being formed essentially by combining [RhI 5  (CO)] -2  X 2  where X is the non-interacting cation tetra butyl ammonium, aqueous HI and acetic acid, the ratio of iodide to rhodium being at least 50 to 1 and the ratio of water to hydrogen cations being about 5 to 100 to 1 in said catalyst system, thereby producing hydrogen and carbon dioxide. 
     
     
       28. The invention as set forth in claim 27 wherein said carbon monoxide reactant is introduced to said catalyst system under pressure of from 250 to 400 torr. 
     
     
       29. The invention as set forth in claim 28 wherein said step of introducing said carbon monoxide reactant is carried out with an inert gas such as nitrogen. 
     
     
       30. The invention as set forth in claim 27 wherein rhodium in the (I) oxidation state is present in said catalyst system. 
     
     
       31. The invention as set forth in claim 27 wherein rhodium in the (III) oxidation state is present in said catalyst system. 
     
     
       32. The invention as set forth in claim 27 wherein said acetic acid is glacial acetic acid. 
     
     
       33. The invention as set forth in claim 27 wherein the concentration of HI in said system is from 1 to 5 molar.

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